EP1661554A1 - Aqueous hair deying composition comprising a block polymer - Google Patents

Aqueous hair deying composition comprising a block polymer Download PDF

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Publication number
EP1661554A1
EP1661554A1 EP05111199A EP05111199A EP1661554A1 EP 1661554 A1 EP1661554 A1 EP 1661554A1 EP 05111199 A EP05111199 A EP 05111199A EP 05111199 A EP05111199 A EP 05111199A EP 1661554 A1 EP1661554 A1 EP 1661554A1
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EP
European Patent Office
Prior art keywords
acid
dyes
block
composition according
dye
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP05111199A
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German (de)
French (fr)
Inventor
Franck Giroud
Lydia Panangatte
Claude Dubief
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LOreal SA
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LOreal SA
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Publication of EP1661554A1 publication Critical patent/EP1661554A1/en
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90—Block copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the present invention relates to an aqueous dyeing composition for keratinous fibers, in particular human keratinous fibers and, more particularly, hair, which comprises at least one dye carrying an ionic charge and a particular block copolymer.
  • the invention also relates to a method for dyeing keratinous fibers, in particular human keratinous fibers and, more particularly, hair, which uses said composition.
  • the dyestuff industry markets a large number of molecules that find their use in various industrial fields.
  • certain carriers of anionic groups such as the sulfonate group, carboxylate, cationic groups such as primary, secondary and tertiary ammonium groups are, because of their affinity with keratin and their dyeing results, used in the formulation of hair coloring products.
  • these molecules can also be introduced into oxidation dye products in order to modulate the shades.
  • the dyes in addition to the properties mentioned above, have a resistance to the alkaline oxidizing medium which characterizes these products.
  • the Applicant has discovered that, surprisingly, the combination of a particular block copolymer with a dye carrying an ionic group increases the solubility in aqueous medium and / or the stability in an oxidizing and reducing medium, and / or the rise and / or the chromaticity on hair of an ionic dye.
  • the Applicant has also discovered that such an association facilitates the unison, that is to say the homogeneous distribution of the color along the same keratin fiber and between the keratinous fibers. And it is this discovery which is at the base of the invention.
  • the dyes may be chosen from acid direct dyes and basic direct dyes.
  • acid dye generally means a dye comprising at least one group COOH, SO 3 H, PO 3 H, or PO 4 H 2 , said groups may exist in the form of salts.
  • salts are generally meant metal salts (for example, alkali or alkaline earth metals), optionally hydroxylated organic amine salts.
  • dyes are also known as anionic dyes.
  • basic dyes a dye having at least one group carrying a positive charge, such as an ammonium group or a quaternized nitrogen atom in a ring.
  • Also suitable in the present invention as the basic dye are direct dyes having one or more optionally substituted amines not directly attached to an aromatic or heterocyclic ring.
  • These dyes are also known as cationic dyes.
  • the acid dyes that may be used in the context of this invention may be chosen from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic quinone dyes, acidic indoamine dyes and acidic natural dyes. mixtures thereof.
  • the basic dyes that may be used in the context of this invention may be chosen from nitrobenzene dyes, azo dyes, azomethine dyes, methine dyes, tetraazapentamethine dyes, anthraquinone dyes, naphthoquinone dyes, benzoquinone dyes, phenotypic dyes, indigo dyes, xanthene dyes, phenanthridine dyes, phthalocyanine dyes, triarylamethane dyes, basic natural dyes and mixtures thereof.
  • direct dyes that can be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772, EP 714954, FR 2 822 696, FR 2 825 702 and FR 2 825 625, FR. 2 822 698, FR 2 822 693, FR 2 822 694, FR 2 829 926, FR 2 807 650, WO 02/078660, WO 02/100834, WO 02/100369, FR 2 844 269.
  • the ionic block of the block copolymer will be an anionic block, in the case where the dye will be a cationic dye (or basic direct dye), and that the ionic block of the block copolymer will be a cationic block, in the case where the dye will be an anionic dye (or acid direct dye).
  • water-soluble nonionic block is generally understood to mean a polymer block comprising at least 80 mol% of at least one water-soluble monomer and optionally up to 20 mol% of one or more insoluble monomers. in water, this or these water-insoluble monomers being distributed randomly within the water-soluble block. This proportion of water insoluble monomers is preferably at most 10 mol% and more preferably less than or equal to 5 mol%.
  • water-soluble compound polymer or monomer
  • the block copolymers used in the compositions of the invention are devoid of saccharide units.
  • the anionic blocks may advantageously result from the polymerization of one or more monomers chosen from monomers bearing at least one carboxylic acid function, monomers bearing at least one sulphonic acid function, monomers carrying at least one functional group phosphonic acid and mixtures thereof.
  • Suitable carboxylic functional monomer (s) may be chosen from (meth) acrylic acid, aspartic acid, 1,4-phenylenediacrylic acid, citraconic acid and trans-cinammic acid. , 4-hydroxy-3-methoxycinnamic acid, p-hydroxycinnamic acid, trans-glutaconic acid, glutamic acid, itaconic acid, linoleic acid, linolenic acid, maleic acid , methylfumaric acid, trans-hex-3-eneedioic acid, trans-trans muconic acid, oleic acid, ricinoleic acid, trans-traumatic acid, vinylbenzoic acid, vinyl glycolic acid.
  • Suitable monomers containing sulfonic function (s) may be chosen from 2-propene-1-sulfonic acid, acrylamidopropanesulphonic acid, 4-styrenesulphonic acid and vinylsulphonic acid.
  • Monomers bearing suitable phosphonic function (s) may be vinylphosphonic acid.
  • the anionic block of the invention is advantageously a block resulting from the polymerization of methacrylic acid optionally in the form of salts and even more preferably of acrylic acid, optionally in the form of salts.
  • the cationic blocks may be blocks of polyamino acids (such as polylysine), blocks of alkanolamine esters of polymethacrylic acid (such as poly (dimethylammonioethyl methacrylate), polyamine blocks (such as polyspermine, polyethyleneimine) or polyvinylpyridine blocks.
  • polyamino acids such as polylysine
  • alkanolamine esters of polymethacrylic acid such as poly (dimethylammonioethyl methacrylate)
  • polyamine blocks such as polyspermine, polyethyleneimine
  • polyvinylpyridine blocks such as polyvinylpyridine blocks.
  • the water-soluble nonionic blocks as mentioned above comprise a large proportion of water-soluble nonionic monomers and optionally non-ionic hydrophobic monomers in small proportions.
  • the nonionic water-soluble monomers may be selected from acrylamide, N-alkylated acrylamides, C 1-6 alkyl or N, N-di-C 1-3, polyethylene glycol acrylate, polyethylene glycol methacrylate, N- vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinyllactams having a cyclic group of 4 to 9 carbon atoms, vinyl alcohol (copolymerized in the form of vinyl acetate and then hydrolysed), ethylene oxide, hydroxyethyl acrylate, methacrylate, hydroxyethyl and hydroxypropyl methacrylate.
  • the water insoluble monomers are chosen from vinyl aromatic compounds such as styrene, 4-butylstyrene, ⁇ -methylstyrene and vinyltoluene, styrene being particularly preferred.
  • the number-average molecular weight of each block of the block copolymer is preferably from 500 to 10 6 , preferably from 800 to 500,000.
  • copolymers that can be used in the context of the invention are poly (acryloxyethyl-trimethylammonium-b-acrylamide methylsulfate), which will be used with an anionic dye, and poly (sodium acrylate-b-acrylamide). ), which will be used with a cationic dye.
  • the block copolymers of the invention can be prepared by the synthesis methods conventionally used to obtain block polymers. For example, anionic polymerization and controlled radical polymerization (see “New Method of Polymer Synthesis", Blackie Academic & Professional, London, 1995, Volume 2, page 1, or Trends Polym. Sci.4, page 183 (1996)). ) which can be carried out according to various processes such as, for example, radical transfer polymerization (Atom Transfer Radical Polymerization or ATRP) (see JACS, 117, page 5614 (1995), de Matyjasezwski and al.), the radical method such as nitroxides (Georges et al., Macromolecules, 1993, 26, 2987).
  • the block copolymers of the invention are generally present in an amount ranging from 0.001% to 20% by weight relative to the total weight of the composition, preferably from 0.01% to 10% by weight.
  • compositions of the invention also comprise a cosmetically acceptable aqueous medium, that is to say a medium compatible with keratinous fibers, such as that hair.
  • the composition may also comprise at least one oxidation base.
  • This oxidation base is advantageously chosen from oxidation bases conventionally used in oxidation dyeing, for example para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
  • the composition may likewise contain one or more couplers conventionally used for dyeing keratinous fibers.
  • couplers there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers.
  • the oxidation base content, in a coupler, when these compounds are present is between 0.001 and 10% by weight of the total weight of the dye composition, and more preferably from 0.005 to 6% by weight.
  • the acid addition salts that can be used are chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and the like. acetates.
  • the cosmetically acceptable aqueous medium generally consists of water or a mixture of water and at least one organic solvent chosen from C 1 -C 4 lower alcohols, such as ethanol, isopropanol, propylene glycol and the like. tert-butanol or n-butanol; polyols such as glycerol, propylene glycol and polyethylene glycols.
  • the pH of the compositions according to the invention is generally between 4 and 11.
  • the pH can be adjusted to the desired value by means of acidifying or alkalinizing agents usually used for dyeing keratinous fibers or else using conventional buffer systems.
  • acidifying agents mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.
  • mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.
  • alkalinizing agents that may be mentioned, for example, ammonia, carbonates alkalines, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of the following formula: wherein W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R a, R b, R c and R d, identical or different, represent a hydrogen atom, an alkyl radical in C 1 -C 4 hydroxyalkyl or C 1 -C 4.
  • composition according to the invention may also comprise at least one oxidizing agent.
  • the presence of such an agent may be particularly useful for obtaining different shades of color from a given dye.
  • the oxidizing agents which may be used are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes, among which may be mentioned peroxidases, oxydos 2-electron reductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.
  • composition according to the invention may further comprise additives chosen from anionic, nonionic and amphoteric surfactants, anionic, nonionic film-forming polymers other than the block polymers described above, cationic or amphoteric conditioning polymers, linear, branched or cyclic silicones, volatile or nonvolatile, organomodified or otherwise, associative or non-associative polymeric thickeners, non-polymeric thickeners, pearlescent agents, opacifiers, dyes or pigments, perfumes, mineral, vegetable and / or synthetic oils, waxes, vitamins, UV filters, anti-radical agents, anti-dandruff agents, preservatives, agents pH stabilizers, solvents and mixtures thereof.
  • additives chosen from anionic, nonionic and amphoteric surfactants, anionic, nonionic film-forming polymers other than the block polymers described above, cationic or amphoteric conditioning polymers, linear, branched or cyclic silicones, volatile or nonvolatile, organo
  • additives are generally present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition.
  • compositions may constitute direct dyeing compositions, that is to say not requiring revelation by developing agents such as oxidizing agents.
  • another subject of the present invention is a method for direct dyeing of keratinous fibers comprising the application of at least one dyeing composition as defined above on dry or wet fibers then the observation of a pause time possibly followed by the rinsing of the fibers.
  • the pause time is generally between a few seconds and 30 minutes, preferably between 3 and 15 minutes.
  • the temperature at which the composition is allowed to act is, in general, between 15 and 220 ° C, more particularly between 15 and 80 ° C, preferably between 15 and 40 ° C.
  • compositions of the invention may also be compositions to be mixed with oxidation dye compositions to modulate the dyeing properties or to be an integral part of an oxidation dye composition.
  • compositions according to the invention even free of oxidation dye (oxidation base / coupler) can also be used in the presence of an oxidizing agent.
  • composition according to the invention is applied to the fibers in the presence of an oxidizing agent that can either be mixed with the composition according to the invention (to obtain a ready-to-use composition) or be applied directly. on the keratin fiber.
  • the oxidizing agent is chosen from the compounds described above.
  • the content of oxidizing agent is in general between 1 and 40% by weight, relative to the weight of the composition ready for use, preferably between 1 and 20% by weight.
  • the composition comprising the oxidizing agent used is an aqueous composition and may be in the form of a solution or an emulsion.
  • the oxidant-free composition is mixed with about 0.5 to 10 equivalents by weight of the oxidizing composition.
  • the pH of the ready-to-use composition is more particularly between 4 and 12, preferably between 7 and 11.5.
  • the pH of the composition may be adjusted by means of an alkalinizing or acidifying agent, chosen in particular from those mentioned above, in the context of the description according to the invention.
  • composition in the presence of the oxidizing agent is therefore applied to dry or wet fibers, for a pause time sufficient to obtain the desired coloration.
  • the pause time and the temperature at which the composition is allowed to act are of the same order as those of the process carried out in the absence of an oxidizing agent.
  • the composition is removed by rinsing with water, optionally followed by washing with a shampoo and rinsing, and optionally drying.
  • the invention relates to the use of a block copolymer as defined above for increasing the solubility in aqueous medium of dyes as defined above, the stability in an oxidizing and reducing medium and for improving the unison on the keratinous fibers.
  • the staining of strands of white hair permed with the dye (Acid Red 18) used at a concentration of 0.6% in water at pH 9 in the presence or absence of 1 % of active material of a diblock copolymer poly (acryloxyethyltrimethylammonium methylsulfate-b-acrylamide) of which each block has a molecular weight of 11 000 and 30 000 respectively (referred to as P1 in the table below).
  • the wicks are read using a Minolta CM3600d colorimeter in the CIE L * a * b * system (specular components included, illuminant D65, angle 10 °).
  • the colored lock using the composition according to the invention is significantly more colored than the control lock and the lock comprising only the acid dye.
  • the chromaticity of the lock obtained by using the composition according to the invention is significantly greater than that obtained by using the acid dye alone.
  • the coloration of the solution remains stable even after 1 hour of rest, which attests the stability of the dye in basic oxidizing medium when it is brought into contact with a block polymer according to the invention.
  • the dye tested is Astrazon Orange R (or Basic Orange 22).
  • an aqueous solution comprising 0.04% dye is added to a test tube.
  • This solution has a cloudy appearance, thus attesting to the poor solubility of this dye in an aqueous medium.

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Abstract

Coloring composition (I) of keratinous fibers, comprising an aqueous medium, comprises: a dye (0.001-5 wt.%) (II) carrying an ionic group; and a copolymer block (III) comprising a nonionic hydrosoluble block and an ionic block having charges opposite to that of the ionic charge carried by the dye. An independent claim is also included for a process for coloring of keratinous fiber, comprising the application of (I) on dry or wet fibers and observing for a period followed by optional rinsing of fibers.

Description

DOMAINE TECHNIQUETECHNICAL AREA

La présente invention concerne une composition aqueuse de coloration des fibres kératiniques, en particulier des fibres kératiniques humaines et, plus particulièrement, des cheveux, qui comprend au moins un colorant porteur d'une charge ionique et un copolymère blocs particulier.The present invention relates to an aqueous dyeing composition for keratinous fibers, in particular human keratinous fibers and, more particularly, hair, which comprises at least one dye carrying an ionic charge and a particular block copolymer.

L'invention concerne, en outre, un procédé de coloration des fibres kératiniques, en particulier des fibres kératiniques humaines et, plus particulièrement, des cheveux, qui met en oeuvre ladite composition.The invention also relates to a method for dyeing keratinous fibers, in particular human keratinous fibers and, more particularly, hair, which uses said composition.

ÉTAT DE LA TECHNIQUE ANTÉRIEURESTATE OF THE PRIOR ART

L'industrie des matières colorantes commercialise un grand nombre de molécules qui trouvent leur utilisation dans divers domaines industriels. Parmi ces molécules, certaines porteuses de groupements anioniques comme le groupe sulfonate, carboxylate, de groupements cationiques comme les groupes ammoniums primaires, secondaires et tertiaires, sont, du fait de leur affinité avec la kératine et de leurs résultats tinctoriaux, utilisées dans la formulation de produits de coloration capillaire.The dyestuff industry markets a large number of molecules that find their use in various industrial fields. Among these molecules, certain carriers of anionic groups such as the sulfonate group, carboxylate, cationic groups such as primary, secondary and tertiary ammonium groups are, because of their affinity with keratin and their dyeing results, used in the formulation of hair coloring products.

Ces molécules peuvent être introduites dans des véhicules aqueux ce qui, après application sur les cheveux, permettra leur transfert. Dans ce cas, il est souhaitable que les colorants soient et restent solubles dans les véhicules considérés, montent rapidement sur les cheveux mais de façon uniforme quelle que soit leur sensibilisation et résistent aux actions répétées des lavages et des expositions à la lumière.These molecules can be introduced into aqueous vehicles which, after application to the hair, will allow their transfer. In this case, it is desirable that the dyes are and remain soluble in the vehicles considered, rise quickly on the hair but in a uniform manner regardless of their sensitization and resist the repeated actions of washing and exposure to light.

Ces molécules peuvent être également introduites dans des produits de coloration d'oxydation afin d'en moduler les nuances. Dans ce cas, il est souhaitable que les colorants, en plus des propriétés mentionnées ci-dessus, présentent une résistance au milieu oxydant alcalin qui caractérise ces produits.These molecules can also be introduced into oxidation dye products in order to modulate the shades. In this case, it is desirable that the dyes, in addition to the properties mentioned above, have a resistance to the alkaline oxidizing medium which characterizes these products.

Il s'avère à l'heure actuelle que les colorants porteurs de groupe(s) ionique(s) ne présentent pas des propriétés totalement satisfaisantes.It currently turns out that the dyes bearing ionic group (s) do not have completely satisfactory properties.

Or, après de longues recherches menées sur la question, la Demanderesse a découvert que, de manière surprenante, l'association d'un copolymère blocs particulier avec un colorant porteur d'un groupe ionique permet d'augmenter la solubilité en milieu aqueux et/ou la stabilité en milieu oxydant et réducteur, et/ou la montée et/ou la chromaticité sur cheveux d'un colorant ionique. La Demanderesse a également découvert qu'une telle association facilitait l'unisson, c'est-à-dire la répartition homogène de la coloration le long d'une même fibre kératinique et entre les fibres kératiniques. Et c'est cette découverte qui est à la base de l'invention.However, after extensive research conducted on the question, the Applicant has discovered that, surprisingly, the combination of a particular block copolymer with a dye carrying an ionic group increases the solubility in aqueous medium and / or the stability in an oxidizing and reducing medium, and / or the rise and / or the chromaticity on hair of an ionic dye. The Applicant has also discovered that such an association facilitates the unison, that is to say the homogeneous distribution of the color along the same keratin fiber and between the keratinous fibers. And it is this discovery which is at the base of the invention.

EXPOSÉ DE L'INVENTIONSTATEMENT OF THE INVENTION

Ainsi, l'invention a, en premier lieu, pour objet, une composition de coloration des fibres kératiniques, comprenant un milieu aqueux physiologiquement acceptable, comprenant .

  • au moins un colorant porteur d'au moins un groupe ionique, ledit colorant étant présent en une teneur allant de 0,001 à 5% en poids par rapport au poids total de la composition ;
  • au moins un copolymère blocs comprenant au moins un bloc non ionique hydrosoluble et au moins un bloc ionique présentant des charges opposées à celle de la charge ionique portée par le colorant.
Thus, the subject of the invention is, first of all, a dyeing composition for keratin fibers, comprising a physiologically acceptable aqueous medium, comprising:
  • at least one dye bearing at least one ionic group, said dye being present in a content ranging from 0.001 to 5% by weight relative to the total weight of the composition;
  • at least one block copolymer comprising at least one water-soluble nonionic block and at least one ionic block having opposite charges to that of the ionic charge carried by the dye.

Selon l'invention, les colorants peuvent être choisis parmi les colorants directs acides et les colorants directs basiques.According to the invention, the dyes may be chosen from acid direct dyes and basic direct dyes.

Rappelons qu'un colorant direct est une substance colorée qui ne nécessite pas l'emploi d'un agent oxydant pour révéler sa couleur. Dans la suite de cet exposé, on utilisera les termes colorants acides et colorants basiques.Remember that a direct dye is a colored substance that does not require the use of an oxidizing agent to reveal its color. In the rest of this talk, we will use the terms acid dyes and basic dyes.

On précise que par colorant acide, on entend généralement un colorant comportant au moins un groupe COOH, SO3H, PO3H, ou PO4H2, lesdits groupes pouvant exister sous forme de sels.It is specified that acid dye generally means a dye comprising at least one group COOH, SO 3 H, PO 3 H, or PO 4 H 2 , said groups may exist in the form of salts.

On précise que, par sels, on entend généralement des sels de métaux (par exemple, métaux alcalins ou alcalino-terreux), des sels d'amine organique éventuellement hydroxylée.It is specified that, by salts, are generally meant metal salts (for example, alkali or alkaline earth metals), optionally hydroxylated organic amine salts.

Ces colorants sont également connus sous l'appellation de colorants anioniques.These dyes are also known as anionic dyes.

On précise, de plus, que par colorants basiques, on entend un colorant présentant au moins un groupe porteur d'une charge positive, tel qu'un groupe ammonium ou un atome d'azote quaternisé dans un cycle.In addition, it is specified that by basic dyes is meant a dye having at least one group carrying a positive charge, such as an ammonium group or a quaternized nitrogen atom in a ring.

Peuvent également convenir dans la présente invention, à titre de colorant basique, bien que de manière non préférée, les colorants directs possédant une ou plusieurs amines éventuellement substituées, non directement liées à un noyau aromatique ou hétérocyclique.Also suitable in the present invention as the basic dye, although not preferably, are direct dyes having one or more optionally substituted amines not directly attached to an aromatic or heterocyclic ring.

Ces colorants sont également connus sous l'appellation de colorants cationiques.These dyes are also known as cationic dyes.

Les colorants acides pouvant être utilisés dans le cadre de cette invention peuvent être choisis parmi les colorants nitrés acides, les colorants azoïques acides, les colorants aziniques acides, les colorants triarylméthaniques acides, les colorants quinoniques acides, les colorants indoaminiques acides les colorants naturels acides et les mélanges de ceux-ci.The acid dyes that may be used in the context of this invention may be chosen from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic quinone dyes, acidic indoamine dyes and acidic natural dyes. mixtures thereof.

A titre illustratif, on peut citer les colorants suivants :

  • Sel de sodium de l'acide 2,4-dinitro-1-naphtol-7-sulfonique ;
  • Acid Orange 3;
  • Acid Yellow 9 / Food Yellow 2;
  • Direct Red 45 / Food Red 13;
  • Acid Black 52;
  • Acid Yellow 36;
  • Sel de sodium de l'acide 1-hydroxy-2-(2',4'-xylyl-5-sufonatoazo)-naphtalène-4-sulfonique /Food Red 1 ;
  • Acid Red 14/ Food Red 3/ Mordant Blue 79;
  • Acid Red 18;
  • Acid Brown 4;
  • Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49;
  • Food Yellow 3 / Pigment Yellow 104;
  • Acid Red 27 / Food Red 9;
  • Acid Orange 10 / Food Orange 4;
  • Acid Red 44;
  • Acid Red 33 / Food Red 12;
  • Sel de sodium de l'acide 1-(3'-nitro-5'-sulfo-6'-oxophénylazo)-8-acétamido-naphtalène-3,6-disulfonique / Food Red 11 ;
  • Sel de sodium de l'acide 1-hydroxy-2-(2'-méthyl phénylazo)-8-acétamido-naphtalene-3,6-disulfonique / Acid Red 35 ;
  • Acid Violet 3;
  • Acid Violet 43;
  • Acid Red 35;
  • Acid Violet 7;
  • Acid Red 135;
  • Acid Yellow 27;
  • Acid Yellow 23 / Food Yellow 4;
  • Acid Yellow 36;
  • 4'-(sulfonato-2'',4''-diméthyl)-bis-(2,6-phénylazo)-1,3-dihydroxy benzène / Acid Orange 24
  • Acid Black 1 (Sel de sodium de l'acide 1-amino-2-(4'-nitrophénylazo)-7-phénylazo-8-hydroxy-naphtalène-3,6-disulfonique) ;
  • (4-((4-méthylphényl) sulfonyloxy)-phényl azo)2,2'-diméthyl-4-((2-hydroxy-5,8-disulfonato)naphtylazo)biphényle / Acid Red 111 ;
  • Food Black 2 ;
  • 1-(4'-sulfonatophénylazo)-4-((2"-hydroxy-3"-acétylamino-6",8"-disulfonato)naphtylazo)-6-sulfonatonaphtalène (sel tétrasodique) / Food Black 1 ;
  • Acide 4-β-hydroxyéthylamino-3-nitro benzènesulfonique ;
  • Acid Blue 9 ;
  • (5',6' ou 7')-sulfonato-6'-méthylquinoléine-2,2',Δ-1,3-indanedione / Acid Yellow 3 ;
  • Sel de sodium de l'acide 4-hydroxy-3((2-méthoxy phényl)-azo)-1-naphtalène sulfonique / Acid Red 4 ;
  • Acide 2-pipéridino 5-nitro benzène sulfonique ;
  • Acide 2(4'-N,N(2"-hydroxyéthyl)amino-2'-nitro)aniline éthane sulfonique ;
  • Acide 4-β-hydroxyéthylamino-3-nitrobenzène sulfonique ;
  • Acid Violet 49 ;
  • Acid Blue 7;
  • Acid Blue 156;
  • Acid Blue 317;
  • Acid Blue 62.
By way of illustration, mention may be made of the following dyes:
  • Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid;
  • Orange Acid 3;
  • Acid Yellow 9 / Food Yellow 2;
  • Direct Red 45 / Food Red 13;
  • Acid Black 52;
  • Acid Yellow 36;
  • Sodium salt of 1-hydroxy-2- (2 ', 4'-xylyl-5-sufonatoazo) -naphthalene-4-sulfonic acid / Food Red 1;
  • Red Acid 14 / Food Red 3 / Mordant Blue 79;
  • Acid Red 18;
  • Acid Brown 4;
  • Orange Acid 7 / Orange Pigment 17 / Solvent Orange 49;
  • Food Yellow 3 / Pigment Yellow 104;
  • Acid Red 27 / Food Red 9;
  • Orange Acid 10 / Food Orange 4;
  • Acid Red 44;
  • Acid Red 33 / Food Red 12;
  • Sodium salt of 1- (3'-nitro-5'-sulfo-6'-oxophenylazo) -8-acetamido-naphthalene-3,6-disulfonic acid / Food Red 11;
  • Sodium salt of 1-hydroxy-2- (2'-methylphenylazo) -8-acetamido-naphthalene-3,6-disulfonic acid / Acid Red 35;
  • Violet Acid 3;
  • Acid Violet 43;
  • Acid Red 35;
  • Acid Violet 7;
  • Acid Red 135;
  • Acid Yellow 27;
  • Acid Yellow 23 / Food Yellow 4;
  • Acid Yellow 36;
  • 4 '- (Sulfonato-2'',4''- dimethyl) -bis- (2,6-phenylazo) -1,3-dihydroxybenzene / Acid Orange 24
  • Acid Black 1 (Sodium salt of 1-amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid);
  • (4 - ((4-methylphenyl) sulfonyloxy) -phenylazo) 2,2'-dimethyl-4 - ((2-hydroxy-5,8-disulfonato) naphthylazo) biphenyl / Acid Red 111;
  • Food Black 2;
  • 1- (4'-sulfonatophenylazo) -4 - ((2 "-hydroxy-3" -acetylamino-6 ", 8" -disulfonato) naphthylazo) -6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1;
  • 4-β-hydroxyethylamino-3-nitro benzenesulfonic acid;
  • Acid Blue 9;
  • (5 ', 6' or 7 ') - sulfonato-6'-methylquinoline-2,2', Δ-1,3-indanedione / Acid Yellow 3;
  • Sodium salt of 4-hydroxy-3 ((2-methoxyphenyl) azo) -1-naphthalenesulfonic acid / Acid Red 4;
  • 2-piperidino 5-nitro benzene sulfonic acid;
  • Acid 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethanesulfonic acid;
  • 4-β-hydroxyethylamino-3-nitrobenzene sulfonic acid;
  • Acid Violet 49;
  • Acid Blue 7;
  • Acid Blue 156;
  • Acid Blue 317;
  • Acid Blue 62.

La plupart de ces colorants sont decrits, en particulier, dans le Color Index publié par The Society of Dyers and Colorists, P.O.Box 244, Perkin House, 82 Grattant Road, Bradford, Yorkshire, BD1 2JBN England.Most of these dyes are described, in particular, in the Color Index published by The Society of Dyers and Colorists, P.O.Box 244, Perkin House, 82 Grattant Road, Bradford, Yorkshire, BD1 2JBN England.

Les colorants basiques pouvant être utilisés dans le cadre de cette invention peuvent être choisis parmi les colorants benzéniques nitrés, les colorants azoïques, les colorants azométhiniques, les colorants méthiniques, les colorants tétraazapentaméthiniques, les colorants anthraquinoniques, les colorants naphtoquinoniques, les colorants benzoquinoniques, les colorants phénotiaziniques, les colorants indigoïdes, les colorants xanthéniques, les colorants phénanthridiniques, les colorants phtalocyanines, les colorants dérivés du triarylaméthane, les colorants naturels basiques et les mélanges de ceux-ci.The basic dyes that may be used in the context of this invention may be chosen from nitrobenzene dyes, azo dyes, azomethine dyes, methine dyes, tetraazapentamethine dyes, anthraquinone dyes, naphthoquinone dyes, benzoquinone dyes, phenotypic dyes, indigo dyes, xanthene dyes, phenanthridine dyes, phthalocyanine dyes, triarylamethane dyes, basic natural dyes and mixtures thereof.

Parmi les colorants directs utilisables selon l'invention on peut citer les colorants cationiques décrits dans les demandes de brevets WO 95/15144, WO 95/01772, EP 714954, FR 2 822 696, FR 2 825 702, FR 2 825 625, FR 2 822 698, FR 2 822 693, FR 2 822 694, FR 2 829 926, FR 2 807 650, WO 02/078660, WO 02/100834, WO 02/100369, FR 2 844 269.Among the direct dyes that can be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772, EP 714954, FR 2 822 696, FR 2 825 702 and FR 2 825 625, FR. 2 822 698, FR 2 822 693, FR 2 822 694, FR 2 829 926, FR 2 807 650, WO 02/078660, WO 02/100834, WO 02/100369, FR 2 844 269.

Parmi ces composés on peut tout particulièrement citer les colorants suivants .

  • chlorure de 1,3-diméthyl-2-[[4-(diméthyl amino)phényl] azo]-1H-Imidazolium ;
  • chlorure de 1,3-diméthyl-2-[(4-aminophényl)azo]-1H-Imidazolium ;
  • méthylsulfate de 1-méthyl-4-[(méthylphényl hydrazono) méthyl]-pyridinium ;
  • Basic Red 22;
  • Basic Red 76;
  • Basic Yellow 57;
  • Basic Brown 16;
  • Basic Blue 41;
  • Basic Blue 67;
  • Basic Brown 1;
  • Basic Brown 4;
  • Basic Red 18;
  • Basic Red 46;
  • Basic Red 104;
  • Basic Red 118;
  • Basic Violet 35;
  • Basic Yellow 45;
  • Basic Yellow 67;
  • Basic Red 14;
  • Basic Yellow 13;
  • Basic Yellow 29;
  • Basic Brown 17;
  • Basic Blue 22;
  • Basic Blue 99 ;
  • 1-N-méthylmorpholiniumpropylamino-4-hydroxyanthraquinone ;
  • Basic Blue 17 ;
  • Basic Red 2 ;
  • Basic Green 1;
  • Basic Violet 3;
  • Basic Violet 14;
  • Basic Blue 7;
  • Basic Blue 26.
Among these compounds, the following dyes may be mentioned in particular.
  • 1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride;
  • 1,3-dimethyl-2 - [(4-aminophenyl) azo] -1H-imidazolium chloride;
  • 1-methyl-4 - [(methylphenylhydrazono) methyl] -pyridinium methylsulfate;
  • Basic Red 22;
  • Basic Red 76;
  • Basic Yellow 57;
  • Basic Brown 16;
  • Basic Blue 41;
  • Basic Blue 67;
  • Basic Brown 1;
  • Basic Brown 4;
  • Basic Red 18;
  • Basic Red 46;
  • Basic Red 104;
  • Basic Red 118;
  • Basic Violet 35;
  • Basic Yellow 45;
  • Basic Yellow 67;
  • Basic Red 14;
  • Basic Yellow 13;
  • Basic Yellow 29;
  • Basic Brown 17;
  • Basic Blue 22;
  • Basic Blue 99;
  • 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone;
  • Basic Blue 17;
  • Basic Red 2;
  • Basic Green 1;
  • Basic Violet 3;
  • Basic Purple 14;
  • Basic Blue 7;
  • Basic Blue 26.

Il est entendu que le bloc ionique du copolymère blocs sera un bloc anionique, dans le cas où le colorant sera un colorant cationique (ou colorant direct basique), et que le bloc ionique du copolymère blocs sera un bloc cationique, dans le cas où le colorant sera un colorant anionique (ou colorant direct acide).It is understood that the ionic block of the block copolymer will be an anionic block, in the case where the dye will be a cationic dye (or basic direct dye), and that the ionic block of the block copolymer will be a cationic block, in the case where the dye will be an anionic dye (or acid direct dye).

Selon l'invention, on précise que par bloc non ionique hydrosoluble, on entend généralement un bloc polymère comprenant au moins 80% en moles d'au moins un monomère hydrosoluble et éventuellement jusqu'à 20% en moles d'un ou plusieurs monomères insolubles dans l'eau, ce ou ces monomères insolubles dans l'eau étant répartis de façon aléatoire au sein du bloc hydrosoluble. Cette proportion de monomères insolubles dans l'eau est de préférence au plus égale à 10% en moles et, mieux encore, inférieure ou égale à 5% en moles.According to the invention, it is specified that water-soluble nonionic block is generally understood to mean a polymer block comprising at least 80 mol% of at least one water-soluble monomer and optionally up to 20 mol% of one or more insoluble monomers. in water, this or these water-insoluble monomers being distributed randomly within the water-soluble block. This proportion of water insoluble monomers is preferably at most 10 mol% and more preferably less than or equal to 5 mol%.

On précise que, par composé hydrosoluble (polymère ou monomère), on entend généralement un composé qui, introduit dans l'eau à 25°C, et si besoin neutralisé, à une concentration en poids égale à 0,1%, permet l'obtention d'une solution ou d'une suspension macroscopiquement homogène et transparente, c'est-à-dire ayant une valeur de transmittance de la lumière, à une longueur d'onde égale à 500 nm, à travers un échantillon de 1 cm d'épaisseur, d'au moins 70%, de préférence d'au moins 80%.It is specified that, by water-soluble compound (polymer or monomer), is generally meant a compound which, introduced into water at 25 ° C, and if necessary neutralized, at a concentration by weight equal to 0.1%, allows the obtaining a macroscopically homogeneous and transparent solution or suspension, that is to say having a light transmittance value, at a wavelength equal to 500 nm, through a sample 1 cm thick, at least 70%, preferably at least 80%.

De préférence, les copolymères blocs utilisés dans les compositions de l'invention sont dénués d'unités saccharidiques.Preferably, the block copolymers used in the compositions of the invention are devoid of saccharide units.

Les blocs anioniques peuvent résulter avantageusement de la polymérisation d'un ou plusieurs monomères choisis parmi les monomères porteurs d'au moins une fonction acide carboxylique, les monomères porteurs d'au moins une fonction acide sulfonique, les monomères porteurs d'au moins une fonction acide phosphonique et les mélanges de ceux-ci.The anionic blocks may advantageously result from the polymerization of one or more monomers chosen from monomers bearing at least one carboxylic acid function, monomers bearing at least one sulphonic acid function, monomers carrying at least one functional group phosphonic acid and mixtures thereof.

Des monomères porteurs de fonction(s) carboxylique(s) appropriés peuvent être choisis parmi l'acide (méth)acrylique, l'acide aspartique, l'acide 1,4-phénylènediacrylique, l'acide citraconique, l'acide trans-cinammique, l'acide 4-hydroxy-3-méthoxycinnamique, l'acide p-hydroxycinnamique, l'acide trans-glutaconique, l'acide glutamique, l'acide itaconique, l'acide linoléique, l'acide linolénique, l'acide maléique, l'acide méthylfumarique, l'acide trans-hex-3-ène dioïque, l'acide trans-trans muconique, l'acide oléique, l'acide ricinoléique, l'acide trans-traumatique, l'acide vinylbenzoïque, l'acide vinylglycolique.Suitable carboxylic functional monomer (s) may be chosen from (meth) acrylic acid, aspartic acid, 1,4-phenylenediacrylic acid, citraconic acid and trans-cinammic acid. , 4-hydroxy-3-methoxycinnamic acid, p-hydroxycinnamic acid, trans-glutaconic acid, glutamic acid, itaconic acid, linoleic acid, linolenic acid, maleic acid , methylfumaric acid, trans-hex-3-eneedioic acid, trans-trans muconic acid, oleic acid, ricinoleic acid, trans-traumatic acid, vinylbenzoic acid, vinyl glycolic acid.

Des monomères porteurs de fonction(s) sulfonique(s) appropriés peuvent être choisis parmi l'acide 2-propène-1-sulfonique, l'acide acrylamidopropane sulfonique, l'acide 4-styrènesulfonique et l'acide vinylsulfonique.Suitable monomers containing sulfonic function (s) may be chosen from 2-propene-1-sulfonic acid, acrylamidopropanesulphonic acid, 4-styrenesulphonic acid and vinylsulphonic acid.

Des monomères porteurs de fonction(s) phosphonique(s) appropriés peuvent être l'acide vinylphosphonique.Monomers bearing suitable phosphonic function (s) may be vinylphosphonic acid.

Il est entendu que les monomères listés ci-dessus peuvent exister sous forme de sels, tels que des sels de sodium, de potassium ou d'ammonium.It is understood that the monomers listed above may exist in the form of salts, such as sodium, potassium or ammonium salts.

Selon l'invention, le bloc anionique de l'invention est avantageusement un bloc résultant de la polymérisation de l'acide méthacrylique éventuellement sous forme de sels et encore plus préférentiellement de l'acide acrylique éventuellement sous forme de sels.According to the invention, the anionic block of the invention is advantageously a block resulting from the polymerization of methacrylic acid optionally in the form of salts and even more preferably of acrylic acid, optionally in the form of salts.

Les blocs cationiques peuvent être des blocs de polyaminoacides(tels que la polylysine), des blocs d'esters alkanolamines de l'acide polyméthacrylique (tels que le poly(diméthylammonioéthylméthacrylate), des blocs de polyamines (telles que la polyspermine, le polyéthylèneimine) ou des blocs de polyvinylpyridine.The cationic blocks may be blocks of polyamino acids (such as polylysine), blocks of alkanolamine esters of polymethacrylic acid (such as poly (dimethylammonioethyl methacrylate), polyamine blocks (such as polyspermine, polyethyleneimine) or polyvinylpyridine blocks.

Les blocs non ioniques hydrosolubles comme mentionnés ci-dessus comprennent une large proportion de monomères hydrosolubles non-ioniques et éventuellement des monomères hydrophobes non-ioniques en faibles proportions.The water-soluble nonionic blocks as mentioned above comprise a large proportion of water-soluble nonionic monomers and optionally non-ionic hydrophobic monomers in small proportions.

Les monomères hydrosolubles non-ioniques peuvent être choisis parmi l'acrylamide, les acrylamides N-alkylés en C1-6 ou N,N-dialkylés en C1-3, l'acrylate de polyéthylèneglycol, le méthacrylate de polyéthylèneglycol, le N-vinylacétamide, le N-méthyl-N-vinylacétamide, le N-vinylformamide, le N-méthyl-N-vinylformamide, les N-vinyllactames comportant un groupe cyclique de 4 à 9 atomes de carbone, l'alcool vinylique (copolymérisé sous forme d'acétate de vinyle puis hydrolysé), l'oxyde d'éthylène, l'acrylate d'hydroxyéthyle, le méthacrylate d'hydroxyéthyle et le méthacrylate d'hydroxypropyle.The nonionic water-soluble monomers may be selected from acrylamide, N-alkylated acrylamides, C 1-6 alkyl or N, N-di-C 1-3, polyethylene glycol acrylate, polyethylene glycol methacrylate, N- vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinyllactams having a cyclic group of 4 to 9 carbon atoms, vinyl alcohol (copolymerized in the form of vinyl acetate and then hydrolysed), ethylene oxide, hydroxyethyl acrylate, methacrylate, hydroxyethyl and hydroxypropyl methacrylate.

Les monomères non-ioniques insolubles dans l'eau peuvent être choisis parmi les monomères vinylaromatiques alkylés ou non, tels que le styrène et les styrènes alkylés comme le 4-butylstyrène, l'a-méthylstyrène et le vinyltoluène ; les diènes tels que le butadiène et le 1,3-hexadiène, et les diènes alkylés tels que l'isoprène et le diméthylbutadiène ; le chloroprène ; les acrylates d' alkyle en C1-10, d'aryle en C6-10 ou d'aralkyle en C6-10, comme par exemple les (méth)acrylates de méthyle, d'éthyle, de n-butyle, de 2-éthylhexyle, de tert-butyle, d'isobornyle, de phényle ou de benzyle ; l'acétate de vinyle ; les vinyléthers de formule CH2=CH-CH2-O-R dans laquelle R représente un groupe alkyle en C1-6 ; l'acrylonitrile ; le chlorure de vinyle ; le chlorure de vinylidène ; la caprolactone ; l'éthylène ; le propylène ; les monomères vinyliques fluorés ou à chaîne perfluorée, tels que les acrylates et méthacrylates de fluoroalkyle ou les α-fluoroacrylates d'alkyle.The water-insoluble nonionic monomers may be chosen from vinylaromatic monomers which may or may not be alkylated, such as styrene and alkylated styrenes, such as 4-butylstyrene, α-methylstyrene and vinyltoluene; dienes such as butadiene and 1,3-hexadiene, and alkylated dienes such as isoprene and dimethylbutadiene; chloroprene; acrylates of C 1-10 alkyl, C 6-10 aryl or C 6-10 aralkyl, such as methyl (meth) acrylates, ethyl, n-butyl, 2-ethylhexyl, tert-butyl, isobornyl, phenyl or benzyl; vinyl acetate; vinyl ethers of the formula CH 2 = CH-CH 2 -OR wherein R represents a C 1-6 alkyl group; acrylonitrile; vinyl chloride; vinylidene chloride; caprolactone; ethylene; propylene; fluorinated or perfluorinated vinyl monomers, such as fluoroalkyl acrylates and methacrylates or alkyl α-fluoroacrylates.

De préférence, les monomères insolubles dans l'eau sont choisis parmi les composés vinyliques aromatiques tels que le styrène, le 4-butylstyrène, l'α-méthylstyrène et le vinyltoluène, le styrène étant particulièrement préféré.Preferably, the water insoluble monomers are chosen from vinyl aromatic compounds such as styrene, 4-butylstyrene, α-methylstyrene and vinyltoluene, styrene being particularly preferred.

La masse moléculaire moyenne en nombre de chaque bloc du copolymère blocs va de préférence de 500 à 106, de préférence de 800 à 500 000.The number-average molecular weight of each block of the block copolymer is preferably from 500 to 10 6 , preferably from 800 to 500,000.

Des copolymères particuliers susceptibles d'être utilisés dans le cadre de l'invention sont le poly(méthylsulfate d'acryloxyéthyl-triméthylammonium-b-acrylamide), qui sera utilisé avec un colorant anionique, et le poly(acrylate de sodium-b-acrylamide), qui sera utilisé avec un colorant cationique.Particular copolymers that can be used in the context of the invention are poly (acryloxyethyl-trimethylammonium-b-acrylamide methylsulfate), which will be used with an anionic dye, and poly (sodium acrylate-b-acrylamide). ), which will be used with a cationic dye.

Les copolymères blocs de l'invention peuvent être préparés par les procédés de synthèse classiquement utilisés pour obtenir des polymères blocs. On peut citer par exemple la polymérisation anionique et la polymérisation radicalaire contrôlée (voir « New Method of Polymer Synthesis », Blackie Academic & Professional, Londres, 1995, volume 2, page 1, ou Trends Polym. Sci.4, page 183 (1996) de C.J Hawker) qui peut être mise en oeuvre suivant différents procédés comme, par exemple, la polymérisation radicalaire par transfert d'atomes (Atom Transfert Radical Polymerisation ou ATRP) (voir JACS, 117, page 5614 (1995), de Matyjasezwski et al.), la méthode des radicaux tels que les nitroxides (Georges et al., Macromolecules, 1993, 26, 2987).The block copolymers of the invention can be prepared by the synthesis methods conventionally used to obtain block polymers. For example, anionic polymerization and controlled radical polymerization (see "New Method of Polymer Synthesis", Blackie Academic & Professional, London, 1995, Volume 2, page 1, or Trends Polym. Sci.4, page 183 (1996)). ) which can be carried out according to various processes such as, for example, radical transfer polymerization (Atom Transfer Radical Polymerization or ATRP) (see JACS, 117, page 5614 (1995), de Matyjasezwski and al.), the radical method such as nitroxides (Georges et al., Macromolecules, 1993, 26, 2987).

On peut aussi utiliser ces procédés pour obtenir un seul des deux types de blocs du copolymère de l'invention, l'autre bloc étant introduit dans le polymère final par l'intermédiaire de l'amorceur utilisé ou bien par réaction de couplage entre les deux blocs.These methods can also be used to obtain only one of the two types of blocks of the copolymer of the invention, the other block being introduced into the final polymer via the initiator used or by a coupling reaction between the two. blocks.

Les copolymères blocs de l'invention sont généralement présents en une quantité allant de 0,001 à 20% en poids par rapport au poids total de la composition, préférentiellement de 0,01 à 10% en poids.The block copolymers of the invention are generally present in an amount ranging from 0.001% to 20% by weight relative to the total weight of the composition, preferably from 0.01% to 10% by weight.

Outre la présence d'un colorant et d'un polymère blocs tel que défini ci-dessus, les compositions de l'invention comprennent également un milieu aqueux cosmétiquement acceptable, c'est-à-dire un milieu compatible avec les fibres kératiniques, telles que les cheveux.In addition to the presence of a dye and a block polymer as defined above, the compositions of the invention also comprise a cosmetically acceptable aqueous medium, that is to say a medium compatible with keratinous fibers, such as that hair.

La composition peut comprendre également au moins une base d'oxydation. Cette base d'oxydation est avantageusement choisie parmi les bases d'oxydation classiquement utilisées en teinture d'oxydation, par exemple les paraphénylènediamines, les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols et les bases hétérocycliques.The composition may also comprise at least one oxidation base. This oxidation base is advantageously chosen from oxidation bases conventionally used in oxidation dyeing, for example para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

La composition peut de même contenir un ou plusieurs coupleurs conventionnellement utilisés pour la teinture de fibres kératiniques. Parmi ces coupleurs, on peut notamment citer les métaphénylènediamines, les méta-aminophénols, les métadiphénols, les coupleurs naphtaléniques et les coupleurs hétérocycliques.The composition may likewise contain one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers.

Généralement, la teneur en base d'oxydation, en coupleur, lorsque ces composés sont présents, est comprise entre 0,001 et 10 % en poids du poids total de la composition tinctoriale, et plus préférentiellement de 0,005 à 6 % en poids.Generally, the oxidation base content, in a coupler, when these compounds are present, is between 0.001 and 10% by weight of the total weight of the dye composition, and more preferably from 0.005 to 6% by weight.

D'une manière générale, les sels d'addition avec un acide utilisables sont notamment choisis parmi les chlorhydrates, les bromhydrates, les sulfates, les citrates, les succinates, les tartrates, les lactates, les tosylates, les benzènesulfonates, les phosphates et les acétates.In general, the acid addition salts that can be used are chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and the like. acetates.

Le milieu aqueux cosmétiquement acceptable est généralement constitué d'eau ou d'un mélange d'eau et d'au moins un solvant organique choisi parmi les alcools inférieurs en C1-C4, tels que l'éthanol, l'isopropanol, le tertio-butanol ou le n-butanol ; les polyols tels que glycérol, le propylèneglycol et les polyéthylèneglycols.The cosmetically acceptable aqueous medium generally consists of water or a mixture of water and at least one organic solvent chosen from C 1 -C 4 lower alcohols, such as ethanol, isopropanol, propylene glycol and the like. tert-butanol or n-butanol; polyols such as glycerol, propylene glycol and polyethylene glycols.

Le pH des compositions selon l'invention est généralement compris entre 4 et 11.The pH of the compositions according to the invention is generally between 4 and 11.

Le pH peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques ou bien encore à l'aide de systèmes tampons classiques.The pH can be adjusted to the desired value by means of acidifying or alkalinizing agents usually used for dyeing keratinous fibers or else using conventional buffer systems.

Parmi les agents acidifiants, on peut citer, à titre d'exemple, les acides minéraux ou organiques comme l'acide chlorhydrique, l'acide orthophosphorique, l'acide sulfurique, les acides carboxyliques comme l'acide acétique, l'acide tartrique, l'acide citrique, l'acide lactique, les acides sulfoniques.Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

Parmi les agents alcalinisants on peut citer, à titre d'exemple, l'ammoniaque, les carbonates alcalins, les alcanolamines telles que les mono-, di- et triéthanolamines ainsi que leurs dérivés, les hydroxydes de sodium ou de potassium et les composés de formule suivante :

Figure imgb0001
dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C1-C4 ; Ra, Rb, Rc et Rd, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 ou hydroxyalkyle en C1-C4.Among the alkalinizing agents that may be mentioned, for example, ammonia, carbonates alkalines, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of the following formula:
Figure imgb0001
 wherein W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R a, R b, R c and R d, identical or different, represent a hydrogen atom, an alkyl radical in C 1 -C 4 hydroxyalkyl or C 1 -C 4.

La composition selon l'invention peut comprendre également au moins un agent oxydant. La présence d'un tel agent peut être notamment utile pour obtenir différentes nuances de couleur à partir d'un colorant donné.The composition according to the invention may also comprise at least one oxidizing agent. The presence of such an agent may be particularly useful for obtaining different shades of color from a given dye.

Les agents oxydants utilisables sont par exemple le peroxyde d'hydrogène, le peroxyde d'urée, les bromates de métaux alcalins, les persels tels que les perborates et persulfates, les peracides et les enzymes oxydases parmi lesquelles on peut citer les peroxydases, les oxydo-réductases à 2 électrons telles que les uricases et les oxygénases à 4 électrons comme les laccases. Le peroxyde d'hydrogène est particulièrement préféré.The oxidizing agents which may be used are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes, among which may be mentioned peroxidases, oxydos 2-electron reductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

La composition selon l'invention peut comprendre en outre des additifs choisis parmi les tensioactifs anioniques, non-ioniques, amphotères, les polymères filmogènes anioniques, non ioniques différents des polymères blocs décrits ci-dessus, les polymères conditionneurs cationiques ou amphotères, les silicones linéaires, ramifiées ou cycliques, volatiles ou non, organomodifiées ou non, les épaississants polymères associatifs ou non, les épaississants non polymères, les agents nacrants, les opacifiants, les colorants ou les pigments, les parfums, les huiles minérales, végétales et/ou synthétiques, les cires, les vitamines, les filtres UV, les agents anti-radicalaires, les antipelliculaires, les conservateurs, les agents de stabilisation de pH, les solvants et leurs mélanges.The composition according to the invention may further comprise additives chosen from anionic, nonionic and amphoteric surfactants, anionic, nonionic film-forming polymers other than the block polymers described above, cationic or amphoteric conditioning polymers, linear, branched or cyclic silicones, volatile or nonvolatile, organomodified or otherwise, associative or non-associative polymeric thickeners, non-polymeric thickeners, pearlescent agents, opacifiers, dyes or pigments, perfumes, mineral, vegetable and / or synthetic oils, waxes, vitamins, UV filters, anti-radical agents, anti-dandruff agents, preservatives, agents pH stabilizers, solvents and mixtures thereof.

L'homme du métier veillera à choisir les éventuels additifs et leur quantité de manière à ce qu'ils ne nuisent pas aux propriétés des compositions de la présente invention.Those skilled in the art will take care to choose the possible additives and their amount so that they do not adversely affect the properties of the compositions of the present invention.

Ces additifs sont généralement présents dans la composition selon l'invention en une quantité allant de 0 à 20% en poids par rapport au poids total de la composition.These additives are generally present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition.

Ces compositions peuvent constituer des compositions de coloration directe, c'est-à-dire ne nécessitant pas de révélation par des agents révélateurs tel que agents oxydants.These compositions may constitute direct dyeing compositions, that is to say not requiring revelation by developing agents such as oxidizing agents.

Ainsi, un autre objet de la présente invention est un procédé de coloration directe des fibres kératiniques comprenant l'application d'au moins une composition de teinture telle que définie ci-dessus sur des fibres sèches ou humides puis l'observation d'un temps de pause suivi éventuellement du rinçage des fibres.Thus, another subject of the present invention is a method for direct dyeing of keratinous fibers comprising the application of at least one dyeing composition as defined above on dry or wet fibers then the observation of a pause time possibly followed by the rinsing of the fibers.

Le temps de pause est généralement compris entre quelques secondes et 30 minutes, de préférence entre 3 et 15 minutes.The pause time is generally between a few seconds and 30 minutes, preferably between 3 and 15 minutes.

La température à laquelle la composition est laissée agir, est, en général, comprise entre 15 et 220°C, plus particulièrement entre 15 et 80°C, de préférence entre 15 et 40°C.The temperature at which the composition is allowed to act is, in general, between 15 and 220 ° C, more particularly between 15 and 80 ° C, preferably between 15 and 40 ° C.

Les compositions de l'invention peuvent être également des compositions à mélanger avec des compositions de coloration d'oxydation afin d'en moduler les propriétés tinctoriales ou faire partie intégrante d'une composition de coloration d'oxydation.The compositions of the invention may also be compositions to be mixed with oxidation dye compositions to modulate the dyeing properties or to be an integral part of an oxidation dye composition.

Les compositions selon l'invention, même exemptes de colorant d'oxydation (base d'oxydation/coupleur) peuvent aussi être mises en oeuvre en présence d'un agent oxydant.The compositions according to the invention, even free of oxidation dye (oxidation base / coupler) can also be used in the presence of an oxidizing agent.

Dans ce cas, on applique sur les fibres la composition selon l'invention, en présence d'un agent oxydant qui peut soit être mélangé à la composition selon l'invention (pour obtenir une composition prête à l'emploi), soit appliqué directement sur la fibre kératinique.In this case, the composition according to the invention is applied to the fibers in the presence of an oxidizing agent that can either be mixed with the composition according to the invention (to obtain a ready-to-use composition) or be applied directly. on the keratin fiber.

De manière classique, l'agent oxydant est choisi parmi les composés décrits auparavant. La teneur en agent oxydant est en général comprise entre 1 et 40 % en poids, par rapport au poids de la composition prête à l'emploi, de préférence entre 1 et 20 % en poids.In a conventional manner, the oxidizing agent is chosen from the compounds described above. The content of oxidizing agent is in general between 1 and 40% by weight, relative to the weight of the composition ready for use, preferably between 1 and 20% by weight.

Généralement, la composition comprenant l'agent oxydant utilisée est une composition aqueuse et peut se trouver sous la forme d'une solution ou encore d'une émulsion.Generally, the composition comprising the oxidizing agent used is an aqueous composition and may be in the form of a solution or an emulsion.

Habituellement, on mélange la composition exempte d'agent oxydant avec environ 0,5 à 10 équivalents en poids de la composition oxydante.Usually, the oxidant-free composition is mixed with about 0.5 to 10 equivalents by weight of the oxidizing composition.

Notons que le pH de la composition prête à l'emploi est plus particulièrement compris entre 4 et 12, de préférence entre 7 et 11,5.Note that the pH of the ready-to-use composition is more particularly between 4 and 12, preferably between 7 and 11.5.

Le pH de la composition peut être réglé au moyen d'un agent alcalinisant ou acidifiant, notamment choisis parmi ceux mentionnés auparavant, dans le cadre de la description selon l'invention.The pH of the composition may be adjusted by means of an alkalinizing or acidifying agent, chosen in particular from those mentioned above, in the context of the description according to the invention.

La composition en présence de l'agent oxydant est donc appliquée sur des fibres sèches ou humides, pendant un temps de pause suffisant pour obtenir la coloration recherchée.The composition in the presence of the oxidizing agent is therefore applied to dry or wet fibers, for a pause time sufficient to obtain the desired coloration.

Le temps de pause et la température à laquelle la composition est laissée agir sont du même ordre que ceux du procédé mis en oeuvre en l'absence d'un agent oxydant.The pause time and the temperature at which the composition is allowed to act are of the same order as those of the process carried out in the absence of an oxidizing agent.

A l'issue du temps de pause, la composition est éliminée par un rinçage à l'eau, suivi éventuellement d'un lavage avec un shampooing et d'un rinçage, puis éventuellement d'un séchage.After the pause time, the composition is removed by rinsing with water, optionally followed by washing with a shampoo and rinsing, and optionally drying.

Enfin, l'invention a trait à l'utilisation d'un copolymère blocs tel que défini ci-dessus pour augmenter la solubilité en milieu aqueux de colorants tels que définis ci-dessus, la stabilité en milieu oxydant et réducteur et pour améliorer l'unisson sur les fibres kératiniques.Finally, the invention relates to the use of a block copolymer as defined above for increasing the solubility in aqueous medium of dyes as defined above, the stability in an oxidizing and reducing medium and for improving the unison on the keratinous fibers.

L'invention va maintenant être décrite en référence aux exemples qui suivent donnés à titre illustratif et non limitatif.The invention will now be described with reference to the following examples given for illustrative and non-limiting.

EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERSDETAILED PRESENTATION OF PARTICULAR EMBODIMENTS Exemple 1Example 1

Dans cet exemple, on a procédé à la coloration de mèches de cheveux blancs permanentés à l'aide du colorant (Acid Red 18) utilisé à la concentration de 0,6 % dans l'eau à pH=9 en présence ou non de 1 % en matière active d'un copolymère diblocs poly(méthylsulfate d'acryloxyéthyl-triméthylammonium-b-acrylamide) dont chaque bloc a pour masse moléculaire respectivement 11 000 et 30 000 (dénommé P1 dans le tableau ci-dessous).In this example, the staining of strands of white hair permed with the dye (Acid Red 18) used at a concentration of 0.6% in water at pH = 9 in the presence or absence of 1 % of active material of a diblock copolymer poly (acryloxyethyltrimethylammonium methylsulfate-b-acrylamide) of which each block has a molecular weight of 11 000 and 30 000 respectively (referred to as P1 in the table below).

Le tableau ci-dessous illustre parfaitement la contribution du polymère diblocs défini ci-dessus en milieu basique dans l'amélioration de la montée du colorant acide.The table below perfectly illustrates the contribution of the diblock polymer defined above in basic medium in improving the rise of the acid dye.

Les mèches sont lues au moyen d'un colorimètre Minolta CM3600d dans le système C.I.E. L*a*b* (composantes spéculaires inclues, illuminant D65, angle 10°).The wicks are read using a Minolta CM3600d colorimeter in the CIE L * a * b * system (specular components included, illuminant D65, angle 10 °).

Plus la valeur de L* est faible, plus la couleur est intense. Traitement L* Cheveux blancs permanentés non colorés 60,5 Acid Red 18 à 0,6 %, pH=9 60,1 P1 + Acid Red 18, pH=9 51,8 The lower the value of L *, the more intense the color. Treatment L * Non colored white permed hair 60.5 Acid Red 18 at 0.6%, pH = 9 60.1 P1 + Acid Red 18, pH = 9 51.8

On constate donc que la mèche colorée en mettant en oeuvre la composition selon l'invention est significativement plus colorée que la mèche témoin et la mèche ne comprenant que le colorant acide.It is therefore found that the colored lock using the composition according to the invention is significantly more colored than the control lock and the lock comprising only the acid dye.

De plus, la chromaticité de la mèche obtenue en mettant en oeuvre la composition selon l'invention est significativement plus importante que celle obtenue en mettant en oeuvre le colorant acide seul.In addition, the chromaticity of the lock obtained by using the composition according to the invention is significantly greater than that obtained by using the acid dye alone.

Exemple 2.Example 2

Dans cet exemple, il a été procédé à des essais destinés à mettre en évidence l'effet protecteur des polymères blocs conformes à l'invention vis-à-vis de colorants instable en milieu oxydant alcalin.
Le colorant testé est le Basic Red 76.In this example, tests have been carried out in order to demonstrate the protective effect of the block polymers in accordance with the invention with regard to unstable dyes in an alkaline oxidizing medium.
The dye tested is the Basic Red 76.

Lors d'un premier essai, on a ajouté dans un tube à essai une solution ammoniacale à 0,04% en poids de colorant à pH= 9 et on a laissé reposer la solution pendant 1 heure.In a first test, an ammonia solution containing 0.04% by weight of dye at pH = 9 was added to a test tube and the solution was allowed to stand for 1 hour.

Lors d'un second essai, on a ajouté dans un tube à essai une solution ammoniacale à 0,04 % en poids de colorant à pH=9 en présence d'un copolymère diblocs poly(acrylate de sodium-b-acrylamide) dont chaque bloc a pour masse moléculaire moyenne en nombre respectivement de 5000 et 30 000 et en présence d'eau oxygénée à 3% et on laisse reposer pendant 1 heure.In a second test, an ammoniacal solution containing 0.04% by weight of dye at pH = 9 was added to a test tube in the presence of a diblock copolymer poly (sodium acrylate-b-acrylamide), each of which The block has a number average molecular weight of 5000 and 30 000 respectively and in the presence of 3% hydrogen peroxide and is left standing for 1 hour.

Pour le premier essai, on constate une dégradation du colorant au bout d'une heure, se traduisant par une perte visible de coloration de la solution.For the first test, there is a degradation of the dye after one hour, resulting in a visible loss of color of the solution.

Pour le second essai, la coloration de la solution reste stable même après 1 heure de repos, ce qui atteste de la stabilité du colorant en milieu basique oxydant lors qu'il est mis en présence d'un polymère blocs conforme à l'invention.For the second test, the coloration of the solution remains stable even after 1 hour of rest, which attests the stability of the dye in basic oxidizing medium when it is brought into contact with a block polymer according to the invention.

EXEMPLE 3.EXAMPLE 3

Dans cet exemple, il a été procédé à des essais destinés à mettre en évidence l'augmentation de la solubilité de colorants difficilement en milieu aqueux grâce à la présence de polymères blocs conformes à l'invention.In this example, tests have been carried out to demonstrate the increase in the solubility of dyes with difficulty in an aqueous medium thanks to the presence of block polymers in accordance with the invention.

Le colorant testé est l'Astrazon Orange R (ou Basic Orange 22).The dye tested is Astrazon Orange R (or Basic Orange 22).

Lors d'un premier essai, on ajoute dans un tube à essai une solution aqueuse comprenant 0,04% de colorant. Cette solution présente un aspect trouble, attestant ainsi de la mauvaise solubilité de ce colorant en milieu aqueux.In a first test, an aqueous solution comprising 0.04% dye is added to a test tube. This solution has a cloudy appearance, thus attesting to the poor solubility of this dye in an aqueous medium.

Lors d'un deuxième essai, on ajoute dans un tube à essai une solution comprenant 0,04% de colorant puis 0,05% en poids d'un copolymère diblocs poly(acrylate de sodium-b-acrylamide) (copolymère de l'exemple 2). La solution résultante est une solution limpide. Ceci atteste ainsi de la capacité des polymères blocs conformes à l'invention d'augmenter la solubilité de colorants difficilement solubles en milieu aqueux.In a second test, a solution comprising 0.04% dye and then 0.05% by weight of a diblock copolymer poly (sodium acrylate-b-acrylamide) (copolymer of example 2). The resulting solution is a clear solution. This attests to the ability of the block polymers according to the invention to increase the solubility of colorants which are difficult to dissolve in an aqueous medium.

Claims (25)

Composition de coloration des fibres kératiniques, comprenant un milieu aqueux physiologiquement acceptable, comprenant . - au moins un colorant porteur d'au moins un groupe ionique, ledit colorant étant présent en une teneur allant de 0,001 à 5% en poids par rapport au poids total de la composition ; - au moins un copolymère blocs comprenant au moins un bloc hydrosoluble non ionique et au moins un bloc ionique présentant des charges opposées à celle de la charge ionique portée par le colorant. A keratin fiber coloring composition comprising a physiologically acceptable aqueous medium comprising at least one dye bearing at least one ionic group, said dye being present in a content ranging from 0.001 to 5% by weight relative to the total weight of the composition; at least one block copolymer comprising at least one water-soluble nonionic block and at least one ionic block having charges opposite to that of the ionic charge carried by the dye. Composition de coloration selon la revendication 1, dans laquelle le colorant est choisi parmi les colorants directs acides, lorsque le bloc ionique est un bloc cationique.The staining composition of claim 1, wherein the dye is selected from acidic direct dyes, when the ionic block is a cationic block. Composition de coloration selon la revendication 2, dans laquelle les colorants directs acides comportent au moins un groupe COOH, SO3H, PO3H, ou PO4H2, lesdits groupes pouvant exister sous forme de sels.The staining composition of claim 2, wherein the acidic direct dyes comprise at least one COOH, SO 3 H, PO 3 H, or PO 4 H 2 group , said groups may exist as salts. Composition de coloration selon la revendication 2 ou 3, dans laquelle les colorants directs acides sont choisis parmi les colorants nitrés acides, les colorants azoïques acides, les colorants aziniques acides, les colorants triarylméthaniques acides, les colorants quinoniques acides, les colorants indoaminiques acides, les colorants naturels acides et les mélanges de ceux-ci.A dyeing composition according to claim 2 or 3, wherein the acidic direct dyes are selected from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic quinone dyes, dyes Indoamino acids, natural acid dyes and mixtures thereof. Composition de coloration selon la revendication 1, dans laquelle le colorant est choisi parmi les colorants directs basiques, lorsque le bloc ionique est un bloc anionique.The staining composition of claim 1, wherein the dye is selected from basic direct dyes, when the ion block is an anionic block. Composition de coloration selon la revendication 5, dans laquelle les colorants directs basiques sont choisis parmi les colorants benzéniques nitrés, les colorants azoïques, les colorants azométhiniques, les colorants méthiniques, les colorants tétraazapentaméthiniques, les colorants anthraquinoniques, les colorants naphtoquinoniques, les colorants benzoquinoniques, les colorants phénotiaziniques, les colorants indigoïdes, les colorants xanthéniques, les colorants phénanthridiniques, les colorants phtalocyanines, les colorants dérivés du triarylaméthane, les colorants naturels basiques et les mélanges de ceux-ci.A staining composition according to claim 5, wherein the basic direct dyes are selected from nitro benzene dyes, azo dyes, azomethine dyes, methine dyes, tetraazapentamethine dyes, anthraquinone dyes, naphthoquinone dyes, benzoquinone dyes, phenotiazine dyes, indigo dyes, xanthene dyes, phenanthridine dyes, phthalocyanine dyes, triarylamethane dyes, basic natural dyes, and mixtures thereof. Composition de coloration selon l'une quelconque des revendications précédentes, dans laquelle le bloc hydrosoluble non-ionique comprend au moins 80% en moles d'au moins un monomère hydrosoluble non-ionique.A staining composition according to any one of the preceding claims, wherein the water-soluble nonionic block comprises at least 80 mol% of at least one water soluble nonionic monomer. Composition de coloration selon l'une quelconque des revendications précédentes, dans laquelle le bloc hydrosoluble non-ionique comprend jusqu'à 20% en moles d'un ou plusieurs monomères insolubles dans l'eau, ce ou ces monomères insolubles dans l'eau étant répartis de façon aléatoire au sein du bloc hydrosoluble non-ionique.A staining composition according to any one of the preceding claims, wherein the water-soluble nonionic block comprises up to 20 mol% of one or more water insoluble monomers, wherein said water insoluble monomer (s) are randomly distributed within the nonionic water soluble block. Composition de coloration selon la revendication 7, dans laquelle le monomère hydrosoluble non-ionique est choisi dans le groupe constitué par l'acrylamide, les acrylamides N-alkylés en C1-6 ou N,N-dialkylés en C1-3, l'acrylate de polyéthylèneglycol, le méthacrylate de polyéthylèneglycol, le N-vinylacétamide, le N-méthyl-N-vinylacétamide, le N-vinylformamide, le N-méthyl-N-vinylformamide, les N-vinyllactames comportant un groupe cyclique de 4 à 9 atomes de carbone, l'alcool vinylique (copolymérisé sous forme d'acétate de vinyle puis hydrolysé), l'oxyde d'éthylène, l'acrylate d'hydroxyéthyle, le méthacrylate d'hydroxyéthyle et le méthacrylate d'hydroxypropyle.Dyeing composition according to claim 7, wherein the nonionic water-soluble monomer is selected from the group consisting of acrylamide, N-alkylated acrylamides, C 1-6 alkyl or N, N-di-C 1-3, the polyethylene glycol acrylate, polyethylene glycol methacrylate, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinyllactams having a cyclic group of 4 to 9 carbon atoms, vinyl alcohol (copolymerized as vinyl acetate and then hydrolysed), ethylene oxide, hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. Composition de coloration selon la revendication 8, dans laquelle le monomère insoluble dans l'eau est choisi dans le groupe constitué par les monomères vinylaromatiques alkylés ou non, les diènes alkylés ou non, le chloroprène, les acrylates d'alkyle en C1-10, d'aryle en C6-10 ou d'aralkyle en C6-10, l'acétate de vinyle, les vinyléthers de formule CH2=CH-CH2-O-R dans laquelle R représente un groupe alkyle en C1-6 ; l'acrylonitrile ; le chlorure de vinyle ; le chlorure de vinylidène ; la caprolactone ; l'éthylène ; le propylène ; les monomères vinyliques fluorés ou à chaîne perfluorée.A staining composition according to claim 8, wherein the water-insoluble monomer is selected from the group consisting of alkylated or unmethylated vinylaromatic monomers, alkylated or non-alkylated dienes, chloroprene, C 1-10 alkyl acrylates. , C 6-10 aryl or C 6-10 aralkyl, vinyl acetate, vinyl ethers of formula CH 2 = CH-CH 2 -OR where R is alkyl C 1-6 ; acrylonitrile; vinyl chloride; vinylidene chloride; caprolactone; ethylene; propylene; fluorinated or perfluorinated vinyl monomers. Composition de coloration selon la revendication 5, dans laquelle le bloc anionique résulte de la polymérisation d'un ou plusieurs monomères choisis parmi les monomères porteurs d'au moins une fonction acide carboxylique, les monomères porteurs d'au moins une fonction acide sulfonique, les monomères porteurs d'au moins une fonction acide phosphonique et les mélanges de ceux-ci.A staining composition according to claim 5, wherein the anionic block results from the polymerization of one or more monomers selected from monomers carrying at least one carboxylic acid function, monomers bearing at least one sulfonic acid function, monomers carrying at least one phosphonic acid function and mixtures thereof. Composition de coloration selon la revendication 11, dans lequel les monomères porteurs d'au moins une fonction acide carboxylique sont choisis dans le groupe constitué par l'acide (méth)acrylique, l'acide aspartique, l'acide 1,4-phénylènediacrylique, l'acide citraconique, l'acide trans-cinammique, l'acide 4-hydroxy-3-méthoxy-cinnamique, l'acide p-hydroxycinnamique, l'acide trans-glutaconique, l'acide glutamique, l'acide itaconique, l'acide linoléique, l'acide linolénique, l'acide maléique, l'acide méthylfumarique, l'acide trans-hex-3-ène dioïque, l'acide trans-trans muconique, l'acide oléique, l'acide ricinoléique, l'acide trans-traumatique, l'acide vinylbenzoïque, l'acide vinylglycolique.The staining composition according to claim 11, wherein the monomers bearing at least one carboxylic acid function are selected from the group consisting of (meth) acrylic acid, aspartic acid, 1,4-phenylenediacrylic acid, citraconic acid, trans-cinamic acid, 4-hydroxy-3-methoxycinnamic acid, p-hydroxycinnamic acid, trans-glutaconic acid, glutamic acid, itaconic acid, linoleic acid, linolenic acid, maleic acid, methylfumaric acid, trans-hex-3-eneedioic acid, trans-trans muconic acid, oleic acid, ricinoleic acid, trans-traumatic acid, vinylbenzoic acid, vinyl glycolic acid. Composition de coloration selon la revendication 11, dans lequel les monomères porteurs d'au moins une fonction acide sulfonique sont choisis dans le groupe constitué par l'acide 2-propène-1-sulfonique, l'acide acrylamidopropane sulfonique, l'acide 4-styrènesulfonique, l'acide vinylsulfonique.The staining composition according to claim 11, wherein the monomers bearing at least one sulfonic acid function are selected from the group consisting of 2-propene-1-sulfonic acid, acrylamidopropanesulfonic acid, 4- styrenesulfonic acid, vinylsulfonic acid. Composition de coloration selon la revendication 2, dans laquelle le bloc cationique est choisi dans le groupe constitué par les blocs de polyaminoacides, les blocs d'esters alkanolamines de l'acide polyméthacrylique, les blocs de polyamines, les blocs de polyvinylpyridine.The staining composition of claim 2 wherein the cationic block is selected from the group consisting of polyamino acid blocks, alkanolamine ester blocks of polymethacrylic acid, polyamine blocks, polyvinylpyridine blocks. Composition de coloration selon l'une quelconque des revendications 1 à 14, dans laquelle le copolymère blocs est présent en une quantité allant de 0,001 à 20% en poids par rapport au poids total de la composition, de préférence, de 0,01 à 10% en poids.Coloring composition according to any one of claims 1 to 14, wherein the block copolymer is present in an amount of from 0.001 to 20% by weight relative to the total weight of the composition, preferably from 0.01 to 10 % in weight. Composition de coloration selon l'une quelconque des revendications 1 à 15, comprenant, en outre, au moins une base d'oxydation choisie parmi les paraphénylènediamines, les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols et les bases hétérocycliques.A coloring composition according to any one of claims 1 to 15, further comprising at least one oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. Composition de coloration selon l'une quelconque des revendications 1 à 16, comprenant, en outre, au moins un coupleur choisi parmi les métaphénylènediamines, les méta-aminophénols, les métadiphénols, les coupleurs naphtaléniques et les coupleurs hétérocycliques.A staining composition according to any one of claims 1 to 16, further comprising at least one coupler selected from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers. Composition de coloration selon l'une quelconque des revendications 1 à 17, présentant un pH allant de 4 à 11.A coloring composition according to any one of claims 1 to 17 having a pH of from 4 to 11. Composition de coloration selon l'une quelconque des revendications 1 à 18, comprenant, en outre, un agent oxydant.The staining composition of any one of claims 1 to 18, further comprising an oxidizing agent. Composition de coloration selon la revendication 19, dans laquelle l'agent oxydant est choisi parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bromates de métaux alcalins, les persels tels que les perborates et persulfates, les peracides, les enzymes oxydases.A coloring composition according to claim 19, wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids, oxidase enzymes . Composition de coloration selon l'une quelconque des revendications 1 à 20, comprenant, en outre, au moins un additif choisi parmi les tensioactifs anioniques, non-ioniques, amphotères, les polymères filmogènes anioniques, non ioniques différents des copolymères blocs tels que définis à la revendication 1, les polymères conditionneurs cationiques ou amphotères, les silicones linéaires, ramifiées ou cycliques, volatiles ou non, organomodifiées ou non, les épaississants polymères associatifs ou non, les épaississants non polymères, les agents nacrants, les opacifiants, les colorants ou les pigments, les parfums, les huiles minérales, végétales et/ou synthétiques, les cires, les vitamines, les filtres UV, les agents anti-radicalaires, les antipelliculaires, les conservateurs, les agents de stabilisation de pH, les solvants et leurs mélanges.A coloring composition according to any one of claims 1 to 20, further comprising at least one additive selected from anionic, nonionic, amphoteric surfactants, anionic, nonionic film-forming polymers other than block copolymers as defined in US Pat. claim 1, cationic or amphoteric conditioning polymers, linear, branched or cyclic silicones, volatile or nonvolatile, organomodified or otherwise, associative or non-associative polymeric thickeners, non-polymeric thickeners, pearlescent agents, opacifiers, dyes or pigments, perfumes, mineral, vegetable and / or synthetic oils, waxes, vitamins, UV filters, anti-radical agents, anti-dandruff, preservatives, pH stabilizers, solvents and mixtures thereof. Procédé de coloration de fibres kératiniques comprenant l'application d'au moins une composition de teinture telle que définie selon l'une quelconque des revendications 1 à 21 sur des fibres sèches ou humides puis l'observation d'un temps de pause suivi éventuellement du rinçage des fibres.A process for dyeing keratinous fibers comprising applying at least one dyeing composition as defined according to any one of Claims 1 to 21 to dry or wet fibers and then observing a pause time possibly followed by rinsing the fibers. Utilisation d'un copolymère blocs tel que défini selon l'une quelconque des revendications 1 à 21 pour améliorer la solubilité en milieu aqueux d'un colorant tel que défini selon l'une quelconque des revendications 1 à 21.Use of a block copolymer as defined in any one of claims 1 to 21 for improving the solubility in aqueous medium of a dye as defined in any one of claims 1 to 21. Utilisation d'un copolymère blocs tel que défini selon l'une quelconque des revendications 1 à 21 pour améliorer la stabilité en milieu oxydant et réducteur d'un colorant tel que défini selon l'une quelconque des revendications 1 à 21.Use of a block copolymer as defined in any one of Claims 1 to 21 for improving the stability in an oxidizing and reducing medium of a dye as defined according to any one of Claims 1 to 21. Utilisation d'une composition telle que définie selon l'une quelconque des revendications 1 à 21, pour améliorer l'unisson de la coloration sur des fibres kératiniques.Use of a composition as defined according to any one of Claims 1 to 21, for improving the unison of the coloration on keratin fibers.
EP05111199A 2004-11-25 2005-11-24 Aqueous hair deying composition comprising a block polymer Withdrawn EP1661554A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1779894A1 (en) * 2005-10-21 2007-05-02 Henkel Kommanditgesellschaft auf Aktien Hair colouring compositions

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
FR2807650A1 (en) 2000-04-18 2001-10-19 Oreal Composition for oxidation-dyeing of keratin fibers, especially hair, contains at least one aminophenyl pyrrolidine as oxidation base and at least one direct colorant
EP1238648A1 (en) * 1999-12-16 2002-09-11 Mitsubishi Pencil Kabushiki Kaisha Cumulative hair-dyeing temporary hair dyes and process for producing the same
FR2822696A1 (en) 2001-04-02 2002-10-04 Oreal NEW TINCTORIAL COMPOSITION FOR DYING KERATINIC FIBERS INCLUDING A SPECIAL DIAZOIC DICATIONIC DYE
FR2822694A1 (en) 2001-04-02 2002-10-04 Oreal NOVEL TINCTORIAL COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A PARTICULAR CATIONIC AZOIC COLORANT
FR2822698A1 (en) 2001-04-03 2002-10-04 Oreal NEW DYE COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A DICATIONIC MONOAZO DYE
FR2822693A1 (en) 2001-04-02 2002-10-04 Oreal NOVEL TINCTORIAL COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A PARTICULAR CATIONIC AZOIC COLORANT
WO2002078660A1 (en) 2001-04-02 2002-10-10 L'oreal Dyeing composition for dyeing keratinous fibres comprising a cationic azo-dye
FR2825625A1 (en) 2001-06-12 2002-12-13 Oreal USE OF DICATIONIC COMPOUNDS IN DYEING OF HUMAN KERATIN FIBERS AND COMPOSITIONS CONTAINING SAME
FR2825702A1 (en) 2001-06-11 2002-12-13 Oreal COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A DIAZOIC DYZOIC SPECIFIC DICATIONIC DYE
WO2002100369A2 (en) 2001-06-11 2002-12-19 L'oreal Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
WO2002100834A1 (en) 2001-06-11 2002-12-19 L'oreal Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
FR2829926A1 (en) 2001-09-26 2003-03-28 Oreal New cationic azo compounds useful for dyeing keratinic fibers, especially human hair
WO2003050184A1 (en) * 2001-12-12 2003-06-19 Rhodia Chimie Cosmetic composition comprising a block copolymer
EP1321128A2 (en) * 2001-12-21 2003-06-25 Hans Schwarzkopf & Henkel GmbH & Co. KG Hair mousse
FR2844269A1 (en) 2002-09-10 2004-03-12 Oreal New cationic azo compounds useful as direct dyes for dyeing human keratinic fibers, especially hair

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
EP1238648A1 (en) * 1999-12-16 2002-09-11 Mitsubishi Pencil Kabushiki Kaisha Cumulative hair-dyeing temporary hair dyes and process for producing the same
FR2807650A1 (en) 2000-04-18 2001-10-19 Oreal Composition for oxidation-dyeing of keratin fibers, especially hair, contains at least one aminophenyl pyrrolidine as oxidation base and at least one direct colorant
FR2822693A1 (en) 2001-04-02 2002-10-04 Oreal NOVEL TINCTORIAL COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A PARTICULAR CATIONIC AZOIC COLORANT
FR2822694A1 (en) 2001-04-02 2002-10-04 Oreal NOVEL TINCTORIAL COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A PARTICULAR CATIONIC AZOIC COLORANT
FR2822696A1 (en) 2001-04-02 2002-10-04 Oreal NEW TINCTORIAL COMPOSITION FOR DYING KERATINIC FIBERS INCLUDING A SPECIAL DIAZOIC DICATIONIC DYE
WO2002078660A1 (en) 2001-04-02 2002-10-10 L'oreal Dyeing composition for dyeing keratinous fibres comprising a cationic azo-dye
FR2822698A1 (en) 2001-04-03 2002-10-04 Oreal NEW DYE COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A DICATIONIC MONOAZO DYE
FR2825702A1 (en) 2001-06-11 2002-12-13 Oreal COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A DIAZOIC DYZOIC SPECIFIC DICATIONIC DYE
WO2002100369A2 (en) 2001-06-11 2002-12-19 L'oreal Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
WO2002100834A1 (en) 2001-06-11 2002-12-19 L'oreal Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
FR2825625A1 (en) 2001-06-12 2002-12-13 Oreal USE OF DICATIONIC COMPOUNDS IN DYEING OF HUMAN KERATIN FIBERS AND COMPOSITIONS CONTAINING SAME
FR2829926A1 (en) 2001-09-26 2003-03-28 Oreal New cationic azo compounds useful for dyeing keratinic fibers, especially human hair
WO2003050184A1 (en) * 2001-12-12 2003-06-19 Rhodia Chimie Cosmetic composition comprising a block copolymer
EP1321128A2 (en) * 2001-12-21 2003-06-25 Hans Schwarzkopf & Henkel GmbH & Co. KG Hair mousse
FR2844269A1 (en) 2002-09-10 2004-03-12 Oreal New cationic azo compounds useful as direct dyes for dyeing human keratinic fibers, especially hair

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"COLOR INDEX", THE SOCIETY OF DYERS AND COLORISTS
"NEW METHOD OF POLYMER SYNTHESIS", vol. 2, 1995, BLACKIE ACADEMIC & PROFESSIONAL, pages: 1
C.J HAWKER: "TRENDS POLYM. SCI.", vol. 4, 1996, pages: 183
GEORGES, MACROMOLECULES, vol. 26, 1993, pages 2987
J.-F. BERRET, G. CRISTOBAL, P. HERVÉ, J. OBERDISSE, I. GRILLO3: "Structure of colloidal complexes obtained from neutral/poly- electrolyte copolymers and oppositely charged surfactants", THE EUROPEAN PHYSICAL JOURNAL E, no. 9, 21 January 2003 (2003-01-21), EDP Sciences / Srpinger-Verlag, XP002334466, Retrieved from the Internet <URL:http://www.edpsciences.org/articles/epje/pdf/2002/13/epje02115.pdf> [retrieved on 20050701] *
JACS, vol. 117, 1995, pages 5614

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1779894A1 (en) * 2005-10-21 2007-05-02 Henkel Kommanditgesellschaft auf Aktien Hair colouring compositions

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